Dripless container coated with fluoroaliphatic siloxanes



Jan. 21, 1969 R. F. HEINE 3,423,234

DRIPLESS CONTAINER COATED WITH FLUOROALIPHATIC sznoxmms Filed April 14,1967 Sheet of 2 }40 I 7 W INVENTOR.

5/67/1420 E HE/NE Jan. 21, 1969 R. F. HEINE 3, 3

' DRIPLEKSS CONTAINER COATED WITH FLUOROALIPHATIC SILOXANES- Filed April14, 1967 Sheet g of 2 7 /0 CONfl/NER L/P PROF/LES Di Qffi? a; Q: L1? LQ; U x} J, E

NVENTOR. 19/67/1420 A flE/ME 4770RNE United States Patent 3,423,234DRIPLESS CONTAINER COATED WITH FLUOROALIPI-IATIC SILOXANES Richard F.Heine, White Bear Lake, Minn., assignor to Minnesota Mining andManufacturing Company, St. Paul, Minn., a corporation of DelawareContinuation-impart of application Ser. No. 467,209, June 28, 1965. Thisapplication Apr. 14, 1967, Ser. No. 630,874 U.S. Cl. 117-124 7 ClaimsInt. Cl. C03c 17/30; C07f 7/12 ABSTRACT OF THE DISCLOSURE Containershaving a substantially dripless orifice, the dripless character beingconferred by a soluble hydrolytically stable polar surface adherentfluoroaliphatic siloxane.

Related appplication This application is a continuation-in-part of my00- pending US. patent application S.N. 467,209, filed June 28, 1965,and now abandoned.

Background Since time immemorial those persons having occasion todispense liquids, especially oils, from container orifices have beentroubled by the well-known nuisance and attendant waste and mess causedby the drops of liquid clinging to exterior container surfaces about theorifice thereof, and frequently running down the container exteriorside. These drops result when a container is reverted to its normalupright storage position following partial inversion during a dispensingoperation.

Heretofore, the art has appreciated that organosiloxanes imparthydrophobic properties to polar substrate surfaces, especially glass(see Melrose US. Pat. No. 3,047,417). The art has also appreciated thatcurable fluoroaliphatic-substituted organosiloxanes have both oleophobicand hydrophobic properties (see Holbrook et al. US. Pat. No. 3,012,006).Such prior art compositions, however, suffer from a number ofdisadvantages for use in making dripless containers. For one thing, theorganosiloxanes, through hydrophobic, are not oleophobic, and thereforecannot be used to produce dripless containers for nonaqueous liquids,e.g., oils. For another, the fluoroaliphatic-substituted siloxanesheretofore used for curable coating surfaces have been hydrolyticallyunstable.

The art has always previously considered it necessary, when producing asiloxane coating on a surface to use a curable siloxane in order toavoid subsequent removal of the coating by liquids contacting the same.Curability has been provided either by using siloxanes free ofhydrolyzable groups which are curable by use of extreme temperatures(e.g., from 175 to 500 F.), or by using siloxanes containinghydrolyzable groups which can 'be subsequently crosslinked, as bycontrolled hydrolysis.

As those in the art will appreciated, the use of high heat to cure isundesirable, particularly because such heat tends to produce bottlebreakage and distortion, so high heat curable siloxanes aredisadvantageous for coating surfaces. On the other hand, in usinghydrolytically curable siloxanes, the treating solutions cannot contactmoisture, such as that in air, during use and. storage, or else, in aPatented Jan. 21, 1969 relatively short time, such siloxane ishydrolyzed into a crosslinked, insoluble, infusible resin completelyunsuited for surface treatment, so these siloxanes, too, aredisadvantageous for coating surfaces.

So far as is known, no one has heretofore produced, from soluble uncuredsiloxanes, hydrolytically stable coatings on polar surfaces whichcoatings are not only oleophobic and hydrophobic, but also dura'blyadherent to such surfaces.

Summary It has now be unexpectedly discovered that post-pour dripping incontainers with polar surfaces in their orifice regions can besubstantially completely eliminated if such orifice region surfaces arecoated with a soluble hydrolytically stable polar surface adherentfluoroaliphatic siloxane.

As used in this application the term container has generic reference tostructures such as vessels, conduits, troughs, bottles, cups, drinkingglasses, flasks, jugs, crooks, drums, tanks, steins, pans, and the like,which are suitable for the storage or dispensing of liquid, especiallyoils of marine or vegetable origin, especially hand-held containers.Container is not limited to closed or closable vessels or the like,although the invention is most applicable to such vessels. Containerscan be constructed of siliceous materials, metals, plastics, cellulosicmaterials, the like substances having polar surfaces.

The term polar, as used herein in reference to a container surface,refers to the fact that such surfaces exert an attractive force towardsmolecules contacting such surfaces when such contacting molecules have,or have readily induced therein, net positively and net negativelycharged regions, so that such molecules, when contacted with suchsurfaces, adhere thereto.

The term lip, lip region or equivalent has reference to that portion ofan aperture to the interior of such a container or to the portion of thecontainer which is used for dispensing the liquid therefrom Whether ornot such is in a special form or position. Thus, for example, a bottleconventionally is equipped with a spout portion in its upper (as when inan upright position), and it is the open end of the spout portion of thebottle which is the lip of the orifice. The terminal region of a spoutwhich joins a containers interior surfaces with its exterior surfaces isspecifically referred to herein as the orifice.

The term hydrolytically stable has reference to the fact thatfluoroaliphatic siloxanes useful in this invention are free ofhydrolyzable groups attached directly to silicon atoms so that suchsiloxanes will not convert, particularly in the presence of atmosphericmoisture from an organic solvent soluble form to an organic solventinsoluble polymeric form.

In accordance with the present invention, it has been discovered thatone can employ soluble, hydrolytically stable, fluoroaliphatic siloxanesfor coating polar surfaced orifice regions of containers and therebyproduce adherent dripless coatings which are uncured, oleophobic andhydrophobic. The adherency of these coatings to such polar surfaces isdemonstrated 'by the fact they can be repeatedly contacted with organicoils or water without appreciably affecting the dripless character of anorifice coated therewith. Thus, for example, a glass bottle Whose mouthis once coated with such a siloxane and which is then filled with an oilcan dispense (as by pouring) the oil therefrom in a substantiallydripless manner in portions over an indefinitely long period of time.The last portion of oil characteristically is dispensed or poured fromthis treated bottle under condition which are as free of dripping as isthe first portion,

Drawing description In the appended drawings:

FIGURE 1 is a side elevational view of the spout region of aconventional liquid container, the lower portion thereof being brokenaway, showing a liquid pouring operation in progress;

FIGURE 2 is a similar view of the spout of FIGURE 1, but showing same atthe moment liquid flow ceases and a drop forms on the container exteriorsurfaces;

FIGURE 3 is a similar view of the spout of FIGURE 2, but showing same asthe drop of liquid subsequently runs down the container exteriorsurfaces;

FIGURE 4 is a side elevational view of the spout region of a liquidcontainer similar to that in FIGURES 1 and 3, but which has been treatedand constructed in accordance with the teachings of the presentinvention, some parts thereof broken away, and showing a pouring oeration in progress;

FIGURE 5 is a similar view of the spout of FIGURE 4 showing same at themoment liquid flow ceases, the liquid running back into the bottleinterior and none collecting on the exterior of the lip;

FIGURE 6 is a similar view of the spout of FIGURE 5, but showing how thecontainer exterior surfaces remain free from liquid following a pouringoperation;

FIGURE 7 is an enlarged sectional view taken axially along the line 77of FIGURE 6 showing a preferred spout construction of the presentinvention;

FIGURE 8 is a view similar to FIGURE 7, but showing another spout lipregion construction;

FIGURE 9 is an enlarged view illustrating constructional details forlips in preferred containers used in the present invention;

FIGURE 10 shows profiles of lip regions in a plurality of containers.

Turning to the figures, there is seen illustrated in FIG- URES 1 through3 a conventional pouring operation from a spout with drop formationoccurring on its lip 14 (see FIGURE 2) as pouring ceases. Thus, as thebottle (not shown) associated with spout 15 is reverted so as to placespout 15 in an upright position, the liquid therein flows back into thelower regions of the bottle and a break in the liquid stream leaving thebottle occurs over lip 14 causing a drop 16 of liquid to remain behindon lip 14 as the liquid flows back into the bottle from lip 14. Thisdrop 16 usually proceeds to travel by gravity down in the inside surfaceof the bottle. Also adhesion between the liquid and container surfacescauses liquid to run down the outside of the bottle.

When, however, a similarly constructed spout 17 with a lip 18 is firsttreated with a fluoroaliphatic siloxane in accordance with the teachingsof this invention and then liquid is poured therefrom as before,substantially all of the liquid in the region of lip 18 flows back downinto the interior portions of the associated vessel (not shown) afterthe bottle is reverted to its original upright position. Substantiallyno liquid residue in the form of drops remains present on the lip 18,and no drops are present to run down the exterior sides when the spout17 is in its normal upright position, as illustrated in FIGURE 6. Alsoadhesion between container surface and liquid is minimized preventingliquid running down the outside of the vessel.

The appearance of a preferred form of bottle lip 28 for use in thepresent invention is illustrated in FIGURE 7. Here the exterior surfaceof a portion of one side of a spout 18 of a bottle (not shown) is on theright side in the drawing, while the interior surface 19 thereof is onthe left side of the drawing, both being apart from the lip 28. Theexterior surface 20 is conveniently substantially parallel to geometricaxis 13 of the spout 18 and/or to interior surface 19. When thedirection of slope of the exterior surface 20 and the interior surface19 forming the lip 28 are both extended as shown by the respective lines21 and 22 in FIGURE 8, it is seen that a projected lip angle 23 isformed which is preferably not more than about This projected lip angle23 is in effect thus formed by the projected meeting of the exteriorsurface 19 with interior surface 20.

The appearance of a lip 12 on a spout 11 which is not especiallysuitable for use in the present invention is illustrated by FIGURE 8. Inthe spout 11, an interior surface 26 is generally in spaced, parallelrelationship to an exterior surface 27. Surfaces 26 and 27 are separatedfrom one another by a substantially flat lip 12 which is substantiallyperpendicular to both the exterior surface 27 and the interior surface26. When an untreated spout 11 is reverted to upright osition followinginversion in a pouring operation, not only does a drop 29 typically rundown the exterior surface 27, but also there is a tendency for droplets31, of smaller size, to form and rest on the lip 28. These smalldroplets 31 are then squeezed out when a cap or stopper (not shown) isplaced thereover. Such additional liquid further adds to the liquid onexterior surface 27 which drains down the outside of the containercoating the surface thereof and eventually Wetting the support for thecontainer.

The preferred geometry of lip constructions taught by the presentinvention is illustrated by FIGURE 9 Where an enlarged (dimensionsproportional) sectional view through the axis of a spout 33 of anupright vessel (not shown) is illustrated. In the lip region 38 of spout33 the exterior surface 36 and the interior surface 37 meet to form arim or lip 38, whose apex region or apex 39 is closer to the exteriorsurface 36 than to the interior surface 37 measured over the lip 38 fromone surface to the other, for example, from exterior surface 36beginning at point 41 to the interior surface 37 ending at point 42. Theapex angle 43 formed by the meeting of lip 38 and apex centerline 40 onthe side of exterior surface 36 is preferably greater than thecorresponding angle 44 formed by the meeting of lip 38 and the apexcenterline 40 on the side of interior surface 37. The horizontal surfaceportions (referring to FIGURE 9) of apex 39 are so designed that theyprovide a bearing or sealing surface for closure means (not shown) suchas a screw-on-type cap or the like, thereby to provide a (demountable)leakproof closure. Those skilled in the art of container manufacturewill readily appreciate that such bearing or sealing surface must be ofsuch a design as to be readily fabricatable in mass production and atthe same time be capable of withstanding repeated application of closuremeans without failure.

Observe that some containers such as hand-held glass bottles (of halfgallon size or less) are commonly equipped with cross-sectionallycircular spouts having orifices and lips of rather small diameter (sayless than 1 /2 or 2 inches); such are known commonly as narrow-mouthbottles. This invention is particularly applicable to such narrow-mouthbottles, though dripless orifices can also be obtained in accordancewith the teachings of the present invention when wide-mouth bottles(those containers with orifices and lips having relatively largerdiameters, for example those with almost or the same as the diameter ofthe bottle) are coated with a fluoroaliphatic siloxane in accordancewith the teachings of this invention. However, to obtain best results inachieving dripless action when using a wide-mouth bottle, it ispreferable to pour only a small stream of liquid from the containerinterior of a lip of a wide-mouth bottle. This is presumably because,when a wide stream is poured out of a fluoroaliphatic siloxane treatedlip of a wide-mouth bottle, the weight of the liquid may in someinstances overcome the oleophobic properties of the treated glasssurface and dripping may occur, although defnitely less than withnontreated containers. However, since, in commerce, bottles are commonlyof the narrow-mouth variety, no particular attention need be paid by theuser to the rate of pouring from a container treated with afluoroaliphatic siloxane in accordance with the teachings of theinvention.

Although the soluble hydrolytically stable polar surface adherentfluoroaliphatic siloxanes useful in this invention impart a usefuldegree of driplessness to container orifices independently of shape, itis preferred to coat with such siloxanes containers having orificeswhich have lip shapes as shown in FIGURE (and as described above).Containers having orifices coated with such siloxanes are preferredproducts of this invention.

Embodiment description The total thickness of a hydrolytically stable,polar surface adherent fluoroaliphatic siloxane coating on containerlips can be very thin. While even a monomolecular layer can produce thedesired results, in practice, coating thicknesses preferably range fromabout 0.002 to as thick as about 10 mils (5 10 cm. to 2.5 10- cm.).Depending on the method of coating, very thin coatings can give erraticresults, while thick coatings tend to be readily abraded away from theorifice surface by container closure means (e.g., screw cap, stopper, orthe like) and are therefore wasteful and without significant utility. Amore preferred range for coaating thicknesses is from about 0.024 to0.24 mil (about 6 10 cm. to 6 10 cm.).

Thus, for fluoroaliphatic siloxanes having a density of about 1.5 acoating weight per sq. cm. of orifice surface area which is preferred isfrom about .0001 gm. to .001 gm. These coating thicknesses and weightsare especially applicable to hydrolytically stable fluoroaliphaticsiloxanes usable in this invention where the amount of fluorinecontained therein is from about 40 to 50% of the total molecular weight.Since the efiiciency of the dripless properties tends to be related tothe quantity of fluorine in the fluoroaliphatic group thereof, suchmaterials which have a higher fluorine content can be used inproportionally thinner coatings while such compounds which have a lowerfluorine content can be used in proportionally thicker coatings toobtain generally equivalent results.

Silanes useful as starting materials for producing solublehydrolytically stable polar surface adherent fluoroaliphatic siloxanesuseful in this invention have the following general formula:

where R is the radical C F Y R, or a monovalent hydrocarbon radicalcontaining less than carbon atoms, such as alkyl, aryl, or the like; Xis chlorine, bromine, fluorine, or an alkoxy radical (substituted orunsubstituted); Y R" is a divalent bridging radical; R" is a divalentalkylene radical or a divalent monohaloalkylene radical containing atleast one and not more than 11 carbon atoms each, the carbon atoms beingattached only to hydrogen atoms or carbon atoms, except for the carbonatom bonded to the silicon atom which may additionally be bonded to nomore than one halogen atom, such halogen being chlorine or bromine; Y isa divalent linking group (linked to both a carbon of C F and a carbon ofR), such as an ester (CO SO ether (-'-O, (CH O, S), amine or amide (CONSO N group; R' is hydrogen or a lower alkyl radical; n is an integerfrom 3 through 18; m is the integer 0 or 1; s is an integer between 1and 6; and q is the integer 1 or 2.

Compounds of Formula 1 are known in the art and can be prepared byconventionally known methods. The term hydrolysis, hydrolyzed products,or equivalent includes hydrolysis accomplished in the presence of wateror of moisture vapor (for example, accomplished in air alone). The termlower has reference to less than seven carbon atoms.

Hydrolysis of the compounds of Formula 1 produces soluble hydrolyticallystable polar surface adherent fluoroaliphatic siloxanes useful forcontainer lip coating in accordance with this invention. Such siloxanesare characterized by the formula.

where R, Y R", R", Y, n, m, and q are as defined above, and r rangesfrom 2 through 7.

The siloxanes of Formula 2 may be linear or cyclic and are usually amixture of both. If linear, the terminal groups are usually a hydrolysisproduct of Formula 1 in which q is 2; the bulk of the material isgenerally of a cyclic structure in which three or more SiO groups arejoined together in alternating SiO structure.

Preferred compounds of Formulas 1 and 2 are those Where R is lower alkyland n ranges from 5 to 10.

To coat the orifice of a container as above described with afluoroaliphatic siloxane of Formula 2, one first suspends (that is,forms a true solution or a colloidal dispersion) such material in anaqueous or nonaqueous liquid carrier or solvent. Because of thegenerally extremely stable character of materials of Formula 2, a verywide variety of liquids can be used as carriers, including, in general,Water and common organic liquids such as alcohols, esters, aldehydes,ketones, hydrocarbons (both aromatic and aliphatic), etc., as well asvarious substituted derivatives thereof, especially the halogenatedanalogues.

In general, it is preferred to use as carriers liquids in whichmaterials of Formula 2 are soluble to at least about 5% by weight (suchas a halogenated hydrocarbon), or in which a relatively stablesuspension can be prepared, such as water because it has been found thatwhen one uses such a solution or suspension of a fluoroaliphaticsiloxane for coating, intimate contact is achievable between thesurfaces of the orifice and the container being coated. Such a contactis essential in order to effect good and uniform deposition of thesiloxane on the container surface.

If the suspension of a fluoroaliphatic siloxane involves the use of anaqueous dispersing liquid medium, then it Will be appreciated that theaqueous medium itself will not Wet siliceous or glass surfaces whichhave already been treated Wtih a lubricant such as a stearate or asilicon as is frequently used in glass bottle manufacture to coat bottlesurfaces When the bottles leave the lehr. For this reason, suchpretreated bottles or containers are preferably coated with a materialof Formula 2 in an organic liquid that will wet the treated surface andprovide the necessary intimate contact described above.

Even if one does not use a glass or siliceous container, but insteademploys acontainer formed of some material, such as metal (e.g., iron,copper or aluminum), or a plastic (e.g., polyethylene, propypropylene,polyethylene terephthalate, polyvinylidene chloride polymer, or thelike), the material of Formula 2 tends to orient so that thefluorocarbon portion is protruding outwardly from the surface and thesilicon containing radical is adjacent or in contact with the surface socoated.

Containers may be treated with a suspension or solution of material ofFormula 2 as above described by any conventional technique, includingdipping, spraying, brushing, swabbing, roller coating, or any othermethod of wet ting the container surface. While only the container lipor spout itself need be coated, it is sometimes convenient and desirableto allow the coated region to extend away from the orifice down thesides of the spout or container to a point where the interior orificesurface comes into continuous, spaced, parallel relationship with theexterior container surface in order to facilitate and enhance retrac- 78 tion of liquid back into the container at the end of a pour- C. at 0.2mm. Hg pressure is separated. This compound ing operation when acontainer is reverted to its normal has the formula: position of rest(generally upright). CBFHCHZCHCISKCHOCIZ Drying following a coatingoperation tends to make the fluoroaliphatic siloxane insoluble so thatit becomes extremely difficult to remove by the mere fiowage or Thecompound having Formula 5 may be hydrolyzed 5 to a siloxane having theformula passage of liquid thereover during a normal pouring op- (6)[CBF1'ICH2CHCISI(CH3)O]Y eration augmented only by the force of gravity.Where r is as defined above, as in the first example and a The followingexamples illustrate preparation of fiuoro treating solution p p usingthat e carbon compounds, container coating solutions and coated 10 Thefellowlng examples are Prevlded to better under containers in accordancewith the present invention: Stand the Present inventioll- TabularPresentationS are used in the interest of conserving space. EXAMPLE AReferring to Table 1, in each example the indicated A fluorocarbonsilane compound is prepared as fiuorochemical (if one is used) is coatedby the indicated lows: To 56.5 grams ofN-allyl-N-ethylperfiuorooctanecoating {method P the l p of a p each esulfonamide in 150 ml. of dry isopropyl ether is added 16 l h P p 6 andconstruction material grams of methyldichlorosilane and 0.1 gram of 5%poware mdlcated: the P e f each P being qeseflbed y dared platinum onCharcoal catalyst The mixture is a reference numeral which refers to aspecific enlarged stirred and refluxed 16 hours, cooled and filtered.The Profile Show G R of the drawmgs' In solvent and excess chlorosilaneare removed under vac- 20 10 Genterhne mdlciates for each Profile themum to leave 67 grams of a White Solid representing a spectrve lnteriorand exterior surfaces. Although the proportions of each profilecorrespond approximately to g s giigf z of the fluorocarbondlchlorosflane of the respective shape of the actual lips involved ineach example, these profiles are not drawn to scale. The par- (3)C8F17SO2N(C2H5)(cH2)3Si(CH3)c12 ticular fluorochemical used is indicatedby a reference number which indicates a specific numbered formula inThlS fiuOIOCafbOIl sllane compound 15 formulatable for the presentspecification reproduced above. In every case treating containersurfaces as follows: 100 ml. of an ether h li treated exhibits driplessproperties. Optimum solution of grams of the fluorocarbon dichlorosilaned i l properties are d d b vthe bi i of of Formula 3 is dropped withstirring into 100 ml. o fluorochemical of compound (2) coated on bottlelips water. After two hours, the ether layer is separated and havingprofile numbers 4, 7 and 8.

TABLE l.-SILICEOUS ORIFICES COATED WITH FLUOROGARBON COMPOUNDSCONTAINDIG SILICON RADICALS Aperture Design Fluorochemical Treating MixDripless Properties Coating Liquid No. Profile Size Material Form.Weight Liqu d Type Method Poured Rating Comments No. (Inches) No.Percent Carrier Min. Oil None. Severe dripping. Min Oil do Do. 4 1. Sol.Spray Min. Oil Fair Drop remains on top of lip. 6 0. $01.... Dip Min.Oil Good. No drop remains on top. 4 3 Sol Swab-.. Veg. Oil... Fair. Fairwhen broad stream poured.

Goo Good when narrow stream poured.- 4 10. 801--.. Brush Alcohol Good4 1. SoL-.. Roller Min. Oil Fair Large drop remains on top when Coated.container reverted to upright. 6 0. $01...- D p Min. 011 do Drop remainson top of hp. 4 5. $01.-.. Dip Veg. Oil..." Good 6 2, SOL-.. Roller Veg.Oil do 1 1 means dia eter. 2 8" means side. 3 1,1,l-trichl0roethane. 4Trichlorotn'fiuoroethane, OClzFCFzOl. 5 Mineral oil availablecommercially under the trademark Nujol."

the ether removed under vacuum to leave a viscous liquid The followingexemplary materials of Formula 2 when fluoroaliphatic siloxane productof the formula: 50 prepared as described in Example A and coated as de-(4) [C8F17SO2N(C2H5)(CHQSSKCHQOL, scribed in Example 1, produce driplesscontainer lip surfaces in accordance with the teachings of the presentwhere r is on the average about 3. Thislprodulct 1s then inventiondissolved in a solvent, such as 1,1,1-trich oroet ane, or achlorofluorocarbon, such as CFCI CF CI for use. The e ls z z z z l- 3)lr foregoing method represents a generally useful method[CIOF2ISOBCH2CHZOQIIIZCHZSI(CH3)O11.

for converting the silanes of Formula 1 to the siloxanes [C F OCH CHS1(C H )O],.

of Formula 2. 'z 15 2 2 2 KQ s) lr Acetone or methyl ethyl ketone arealso solvents for [C F S(CH Si(CH )O] this siloxane product of Formula4, but are less desirable [C F CH N(CH )CH CH CH Si(CI-I )O] because oftheir associated flammability hazard. Generally, [C F CONHCH CH CH Si((11.1 )O

such treating solutions of this siloxane product of For-[09F19QH2CH2Si(CH3)0]r mula 4 preferably contain from 0.05 to 10.0weight per- [C8F17SO2N(CH3)(CH2)11Si(CH3)O]r cent thereof. This treatingsolutlon 1s then used for the [cqFlscHzcHzsucHgoh coating of an orifice.I claim: 7

EXAMP B 1. In a container of the type having polar exterior Afluorocarbon silane compound is prepared a f l. surfaces and polarinterior surfaces in spaced relationl A i t f 300 grams f C F SO CL 50grams ship to one another which meet at the end of a pouring of vinylmethyl dichlorosilane, and 1.5 grams of bis(isoneck to form a lip, theimprovement which comprises butyronitrile) is stirred and heated slowlyto 80 C. in coating said lip with a soluble, polar surface adherent, anoil bath. Gas evolution begins at about C. and hydrolytically stablefiuoroaliphatic siloxane of the forcontinues until the reaction isterminated, about four l hours. The product after cooling is vacuumdistilled. Un-

reacted starting materials are removed in a forecut, then I: r

CnFzn+iYmR"SiO 210 grams of product having a boiling point of -105 75 9Where R' is the radical c F Y R", or a monovalent hydrocarbon radicalcontaining less than 15 carbon atoms;

Y R" is a divalent bridging radical;

R" is a divalent alkylene radical or a divalent monohaloalkylene radicalcontaining at least one and not more than 11 carbon atoms each, thecarbon atoms being attached to hydrogen atoms or carbon atoms, exceptfor the carbon atom bonded to the silicon atom which may additionally bebonded to no more than one halogen atom, such halogen being chlorine orbromine;

Y is a divalent linking group linked to both a carbon of C F- and acarbon of R";

n is an integer from 3 through 18;

m is the integer or 1;

q is the integer 1 or 2; and

r ranges from 2 through 7.

2. The container of claim 1 in which, as respects said lip, the apex iscloser to said exterior surface than to said interior surface measuredover said lip from one surface to the other, the angle formed by themeeting of said lip and the apex on the side of said exterior surfacebeing greater than the corresponding angle formed by the meeting of saidlip and the apex on the side of said interior surface.

3. The container of claim 1 wherein said lip surfaces are siliceous.

4. The container of claim 1 wherein said polar exterior surface portionsadjacent said lip have radially extending but spirally andcircumferentially located rib-like projections adapted for threadablyreeciving a mating cap.

5. In a method for rendering the lips of a polar surfaced orifice regionof a container hydrophobic and oleophobic, the improvement whichcomprises contacting such lips with a solution having suspended thereina soluble hydrolytically stable polar surface adherent fluoroaliphaticsiloxane of the formula:

[ I H JI Where:

R is the radical C F Y R", or a monovalent hydrocarbon radicalcontaining less than 15 carbon atoms;

Y R" is a divalent bridging radical;

R" is a divalent alkylene radical or a divalent monohaloalkylene radicalcontaining at least one and not more than 11 carbon atoms each, thecarbon atoms being attached to hydrogen atoms or carbon atoms, exceptfor the carbon atom bonded to the silicon atom which may additionally bebonded to no more than one halogen atom, such halogen being chlorine orbromine;

Y is a divalent linking group linked to both a carbon of C F and acarbon of R";

n is an integer from 3 through 18;

m is the integer 0 or 1;

q is the integer 1 or 2; and

r ranges from 2 through 7; and evaporating the carrier liquid.

6. The process of claim 5 wherein the container is characterized byhaving a lip whose apex is closer to said exterior surface than to saidinterior surface measured over said lip from one surface to the other,the angle formed by the meeting of said lip and the apex on the side ofsaid exterior surface being greater than the corresponding angle formedby the meeting of said lip and the apex on the side of said interiorsurface.

7. The process of claim 5 wherein the container is formed of a siliceousmaterial.

References Cited UNITED STATES PATENTS 3,012,006 12/1961 Holbrook et al.l17-161 X 3,047,417 6/1962 Melrose 11743 X 3,074,548 1/1963 Parks 117-953,179,290 4/1965 Whitney 22257l RALPH S. KENDALL, Primary Examiner.

HERBERT (ZOHEN, Assistant Examiner.

U.S. Cl. X.-R.

